Composite film of 6FPBO and triple-shelled mesoporous silica hollow spheres and its preparation and use

Patent metadata

Field	Value
Publication number	US-11965070-B2
Application number	US-202117453102-A
Country	US
Kind code	B2
Filing date	Nov 1, 2021
Priority date	Nov 12, 2020
Publication date	Apr 23, 2024
Grant date	Apr 23, 2024

Abstract

The disclosure relates to the field of electronic materials, and in particular to a composite film of fluorinated polybenzoxazole (6FPBO) and triple-shelled mesoporous silica hollow spheres, and to its preparation and use. The composite film comprises fluorinated polybenzoxazole as a matrix and amino-functionalized triple-shelled mesoporous silica hollow spheres which are dispersed in the fluorinated polybenzoxazole matrix. A mass ratio of (amino-functionalized triple-shelled mesoporous silica hollow spheres)/(fluorinated polybenzoxazole) is 1/100 to 5/100. The composite film has excellent thermal stability and a lower dielectric constant.

First claim

What is claimed is:

1. A composite film of fluorinated polybenzoxazole and triple-shelled mesoporous silica hollow spheres, comprising:
fluorinated polybenzoxazole as a matrix, and
amino-functionalized triple-shelled mesoporous silica hollow spheres, which are dispersed in the fluorinated polybenzoxazole matrix,

wherein, a mass ratio of (amino-functionalized triple-shelled mesoporous silica hollow spheres)/(fluorinated polybenzoxazole) is 1/100 to 5/100.

2. A method for preparing the composite film according to claim 1 , the method comprising:
mixing the amino-functionalized triple-shelled mesoporous silica hollow spheres with 2,2-bis(3-amino-4-hydroxyphenyl)-hexafluoropropane, terephthalic acid, polyphosphoric acid, and stannous chloride to conduct an in-situ polymerization reaction so as to obtain a first intermediate product system after removal of water; and
subjecting the first intermediate product system to heat treatment and then to a film formation process.

3. The method according to claim 2 , wherein, the amino-functionalized triple-shelled mesoporous silica hollow spheres are prepared by:
mixing aqueous ammonia, a porogen, anhydrous ethanol, and water to form a mixture, to which tetraethyl orthosilicate and 1,2-bis(triethoxysilyl)ethane are added in three portions to conduct a sol-gel reaction so as to obtain triple-shelled silica solid spheres;
subjecting a mixture of the obtained triple-shelled silica solid spheres and water to a hydrothermal reaction and then to calcination, so as to obtain triple-shelled mesoporous silica hollow spheres; and
mixing the obtained triple-shelled mesoporous silica hollow spheres with anhydrous ethanol and an amination agent for amino modification so as to obtain the amino-functionalized triple-shelled mesoporous silica hollow spheres.

4. The method according to claim 3 , wherein, tetraethyl orthosilicate and 1,2-bis(triethoxysilyl)ethane are each added in three equal portions to the mixture of aqueous ammonia, the porogen, anhydrous ethanol, and water.

5. The method according to claim 2 , wherein, the amino-functionalized triple-shelled mesoporous silica hollow spheres are mixed with 2,2-bis(3-amino-4-hydroxyphenyl)-hexafluoropropane, terephthalic acid, polyphosphoric acid, and stannous chloride in a mixing ratio (mass ratio) of (0.0727-0.3635):(5-6):(2.27-2.30):(25.95-26.50):(0.03-0.04).

6. The method according to claim 2 , wherein, the in-situ polymerization reaction is conducted under vacuum at a temperature of 90 to 95° C. for a time period of 2 to 3 h.

7. The method according to claim 2 , wherein, the heat treatment, to which the first intermediate product system is subjected, is conducted in a protective gas atmosphere by heating to and maintained at 90° C. for 1 h, 130° C. for 12 h, 150° C. for 12 h, then 165° C. for 12 h, and finally 180° C. for 8 to 9 h.

8. The method according to claim 2 , wherein, the film formation process is carried out under a pressure of 10 to 12 MPa at a temperature of 200 to 220° C. for a time period of 30 to 60 min.

Assignees

• Univ East China Science & Tech

Inventors

• Zhuang Qixin
• Zhang Zhe
• Liu Xiaoyun
• Xu Jian
• Wang Wentao
• Wu Zeyang
• Wu Xiaohan
• Li Lihui

Classifications

• C08L79/04

  Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors · CPC title

• H10W74/47

  comprising organic materials, e.g. plastics or resins · CPC title

• C08J5/18 Primary

  Manufacture of films or sheets · CPC title

• C01B33/148 Primary

  Concentration; Drying; Dehydration; Stabilisation; Purification {(C01B33/1465 takes precedence)} · CPC title

• C08K7/26

  Silicon- containing compounds · CPC title